TWI666302B - Etchant composition for indium oxide layer, method of etching, an array substrate for liquid crystal display and manufacturing method thereof using the same - Google Patents
Etchant composition for indium oxide layer, method of etching, an array substrate for liquid crystal display and manufacturing method thereof using the same Download PDFInfo
- Publication number
- TWI666302B TWI666302B TW105102697A TW105102697A TWI666302B TW I666302 B TWI666302 B TW I666302B TW 105102697 A TW105102697 A TW 105102697A TW 105102697 A TW105102697 A TW 105102697A TW I666302 B TWI666302 B TW I666302B
- Authority
- TW
- Taiwan
- Prior art keywords
- oxide layer
- indium oxide
- etchant composition
- etching
- layer
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30604—Chemical etching
Abstract
公開了用於蝕刻氧化銦層的蝕刻劑組合物，蝕刻方法，使用它們的液晶顯示器陣列基板及其製造方法，所述蝕刻劑組合物包括硝酸或亞硝酸、氯化合物、硝酸鹽化合物和水。 An etchant composition for etching an indium oxide layer, an etching method, a liquid crystal display array substrate using the same, and a manufacturing method thereof are disclosed. The etchant composition includes nitric acid or nitrous acid, a chlorine compound, a nitrate compound, and water.
Description
本發明涉及用於蝕刻氧化銦層的蝕刻劑組合物，蝕刻方法，和使用它們的液晶顯示器陣列基板及其製造方法，更具體地說，涉及包括硝酸或亞硝酸、氯化合物、硝酸鹽化合物和水的用於蝕刻氧化銦層蝕刻劑組合物，以及使用它們的液晶顯示器陣列基板及其製造方法。 The present invention relates to an etchant composition for etching an indium oxide layer, an etching method, and a liquid crystal display array substrate using the same, and a manufacturing method thereof, and more particularly, it includes nitric acid or nitrous acid, a chlorine compound, a nitrate compound, and An etchant composition for etching an indium oxide layer using water, a liquid crystal display array substrate using the same, and a manufacturing method thereof.
在平板顯示器之中，液晶顯示(LCD)裝置由於它的解析度高、圖像清晰、耗電低和顯示螢幕薄受到了注意。通常可用作驅動LCD裝置的電子電路是薄膜電晶體(TFT)電路，特別是對顯示螢幕的每個像素形成TFT。利用TFT作為開關元件的TFT-LCD包括設置在基質中的TFT基板、佈置成面向所述基板的彩色濾光片基板和介於上述兩個基板之間的液晶材料。製作TFT-LCD的方法包括製備TFT基板、形成彩色濾光片基板、液晶盒加工和模組加工。 因此，為了實現準確和清晰的圖像，所述TFT基板和所述彩色濾光片基板的製作被認為是非常重要的。 Among flat panel displays, liquid crystal display (LCD) devices have attracted attention due to its high resolution, sharp images, low power consumption, and thin display screen. An electronic circuit commonly used to drive an LCD device is a thin film transistor (TFT) circuit, and in particular, a TFT is formed for each pixel of a display screen. A TFT-LCD using a TFT as a switching element includes a TFT substrate provided in a matrix, a color filter substrate arranged to face the substrate, and a liquid crystal material interposed between the two substrates. The method for manufacturing a TFT-LCD includes preparing a TFT substrate, forming a color filter substrate, processing a liquid crystal cell, and processing a module. Therefore, in order to achieve accurate and clear images, the fabrication of the TFT substrate and the color filter substrate is considered to be very important.
所述LCD裝置包括傳輸掃描信號的閘極線或掃描信號線、傳輸圖像信號的資料線或圖像信號線、與所述閘極線和資料線連接的TFT、和與所述TFT連接的像素電極。 The LCD device includes a gate line or a scanning signal line for transmitting a scanning signal, a data line or an image signal line for transmitting an image signal, a TFT connected to the gate line and the data line, and a TFT connected to the TFT. Pixel electrode.
所述LCD裝置如下製造：在基板上形成用於閘極線和資料線的金屬層，蝕刻所述金屬層，形成與TFT連接的像素電極，施加光刻膠，並形成圖案。因而，與所述像素電極層連接或裸露的所述閘極線或源/汲極線在所述像素電極形成圖案的過程中可能變形。 The LCD device is manufactured by forming a metal layer for a gate line and a data line on a substrate, etching the metal layer, forming a pixel electrode connected to a TFT, applying a photoresist, and forming a pattern. Therefore, the gate line or the source / drain line connected or exposed to the pixel electrode layer may be deformed during the patterning process of the pixel electrode.
為了解決這個問題，用於像素電極的材料的種類必須不同於用於所述閘極或源/汲極的金屬。具體而言，所述像素電極的材料包括具有光學透明度和高導電性的氧化銦層，例如a-ITO、IZO、IGZO或ITZO。 To solve this problem, the kind of material used for the pixel electrode must be different from the metal used for the gate or source / drain. Specifically, the material of the pixel electrode includes an indium oxide layer having optical transparency and high conductivity, such as a-ITO, IZO, IGZO, or ITZO.
最近，所述氧化銦層被形成為具有更精細的圖案並且更厚，以便實現具有高解析度和快速回應速度的顯示裝置。 Recently, the indium oxide layer is formed to have a finer pattern and is thicker in order to realize a display device with high resolution and fast response speed.
韓國專利申請公佈No.10-2012-0093499公開了用於蝕刻氧化銦層的蝕刻劑組合物，但是問題在於使用了環境有害的硫酸，況且，不能蝕刻厚氧化銦層。 Korean Patent Application Publication No. 10-2012-0093499 discloses an etchant composition for etching an indium oxide layer, but the problem is that environmentally harmful sulfuric acid is used, and further, a thick indium oxide layer cannot be etched.
[引用列表] [Quote list]
[專利文獻] [Patent Literature]
專利文件：韓國專利申請公佈No.10-2012-0093499 Patent Document: Korean Patent Application Publication No. 10-2012-0093499
因此，本發明的目的是提供用於蝕刻氧化銦層的蝕刻劑組合物，其可以蝕刻氧化銦層同時最小化對佈置在所述氧化銦層之下的下部金屬層的損害。 Therefore, an object of the present invention is to provide an etchant composition for etching an indium oxide layer, which can etch the indium oxide layer while minimizing damage to a lower metal layer disposed under the indium oxide layer.
本發明的另一個目的是提供用於蝕刻氧化銦層的蝕刻劑組合物，其具有蝕刻厚氧化銦層的高能力，因此能夠形成精細圖案，並且其還可以降低所述氧化銦層的側蝕距離，從而防止由於過蝕刻所述圖案導致的線條損失。 Another object of the present invention is to provide an etchant composition for etching an indium oxide layer, which has a high ability to etch a thick indium oxide layer, so that it can form a fine pattern, and it can also reduce side etching of the indium oxide layer. Distance to prevent line loss due to over-etching the pattern.
為了實現上述目的，本發明提供了用於蝕刻氧化銦層的蝕刻劑組合物，包括：基於其總重量，5至12wt%的硝酸或亞硝酸，0.01至5wt%的氯化合物，0.01至3wt%的硝酸鹽化合物，和餘量的水，使得所述蝕刻劑組合物的總重量是100wt%。 To achieve the above object, the present invention provides an etchant composition for etching an indium oxide layer, including: 5 to 12 wt% nitric acid or nitrous acid, 0.01 to 5 wt% chlorine compounds, and 0.01 to 3 wt% based on the total weight thereof. Nitrate compound, and the balance of water such that the total weight of the etchant composition is 100% by weight.
另外，本發明提供了蝕刻氧化銦層的方法，所述方法包括：(1)在基板上形成氧化銦層，(2)在所述氧化銦層上選擇性地留下光敏材料，和(3)利用本發明的蝕刻劑組合物蝕刻所述氧化銦層。 In addition, the present invention provides a method for etching an indium oxide layer, the method comprising: (1) forming an indium oxide layer on a substrate, (2) selectively leaving a photosensitive material on the indium oxide layer, and (3 ) Etching the indium oxide layer with the etchant composition of the present invention.
另外，本發明提供了製造液晶顯示器的陣列基板的方法，所述方法包括：(1)在基板上形成閘極線，(2)在包括所述閘極線的基板上形成閘極絕緣層，和(3)在所述閘極絕緣層上形成氧化物半導體層，(4)在所述氧化物半導體層上形成源極電極和汲極電極，和(5)形成與所述汲極電極連接的像素電極，其中(5)包括形成氧化銦層和 利用蝕刻劑組合物蝕刻所述氧化銦層，從而形成所述像素電極，並且所述蝕刻劑組合物是本發明的蝕刻劑組合物。 In addition, the present invention provides a method of manufacturing an array substrate for a liquid crystal display, the method comprising: (1) forming a gate line on a substrate, (2) forming a gate insulating layer on a substrate including the gate line, And (3) forming an oxide semiconductor layer on the gate insulating layer, (4) forming a source electrode and a drain electrode on the oxide semiconductor layer, and (5) forming a connection with the drain electrode A pixel electrode, wherein (5) includes forming an indium oxide layer and The indium oxide layer is etched with an etchant composition to form the pixel electrode, and the etchant composition is an etchant composition of the present invention.
另外，本發明提供了通過上述方法製造的液晶顯示器陣列基板。 In addition, the present invention provides a liquid crystal display array substrate manufactured by the above method.
根據本發明，用於蝕刻氧化銦層的蝕刻劑組合物具有蝕刻厚氧化銦層的高能力，從而形成精細圖案，並且通過抑制所述氧化銦層的過蝕刻而有效防止線條的損失。 According to the present invention, the etchant composition for etching an indium oxide layer has a high ability to etch a thick indium oxide layer, thereby forming a fine pattern, and effectively prevents line loss by suppressing over-etching of the indium oxide layer.
此外，根據本發明，所述用於蝕刻氧化銦層的蝕刻劑組合物可蝕刻氧化銦層同時最小化對所述氧化銦層之下的下部金屬層的損害。 In addition, according to the present invention, the etchant composition for etching an indium oxide layer can etch the indium oxide layer while minimizing damage to a lower metal layer below the indium oxide layer.
本發明的上述和其他目的、特徵和優點將從以下結合附圖的詳細說明中更清楚地理解，其中：圖1是掃描電子顯微鏡(SEM)圖像，示出了氧化銦層的側蝕距離；圖2是SEM圖像，示出了沒有來自氧化銦層的殘渣；圖3是SEM圖像，示出了從氧化銦層產生的殘渣；圖4是SEM圖像，示出了沒有對氧化銦層之下的鋁/鉬層的損害；和圖5是SEM圖像，示出了對氧化銦層之下的鋁/鉬層的損害。 The above and other objects, features, and advantages of the present invention will be more clearly understood from the following detailed description in conjunction with the accompanying drawings, in which: FIG. 1 is a scanning electron microscope (SEM) image showing the side etching distance of the indium oxide layer Figure 2 is a SEM image showing no residue from the indium oxide layer; Figure 3 is a SEM image showing a residue from the indium oxide layer; Figure 4 is a SEM image showing no oxidation against Damage to the aluminum / molybdenum layer under the indium layer; and FIG. 5 is a SEM image showing damage to the aluminum / molybdenum layer under the indium oxide layer.
在下文中，將給出本發明的詳細說明。 Hereinafter, a detailed description of the present invention will be given.
本發明提出了用於蝕刻氧化銦層的蝕刻劑組合物，其包括，基於所述蝕刻劑組合物的總重量，5至12wt%的硝酸或亞硝酸，0.01至5wt%的氯化合物，0.01至3wt%的硝酸鹽化合物，和餘量的水，使得所述蝕刻劑組合物的總重量是100wt%。 The present invention proposes an etchant composition for etching an indium oxide layer, which includes, based on the total weight of the etchant composition, 5 to 12 wt% of nitric acid or nitrous acid, 0.01 to 5 wt% of a chlorine compound, and 0.01 to 3 wt% of the nitrate compound, and the balance of water such that the total weight of the etchant composition is 100 wt%.
雖然常規用於液晶顯示器中像素電極的氧化銦層具有500Å或更小的厚度，但為了實現具有快速回應速度和高解析度的液晶顯示器，它需要變得更厚。因此，所述氧化銦層的厚度必須設為1300Å或更厚。 Although the indium oxide layer conventionally used for a pixel electrode in a liquid crystal display has a thickness of 500 Å or less, in order to realize a liquid crystal display having a fast response speed and a high resolution, it needs to be thicker. Therefore, the thickness of the indium oxide layer must be set to 1300 Å or more.
隨著氧化銦層變厚，蝕刻所述氧化銦層以便形成像素電極所需要的時間段增加。因而，不僅在縱向而且在橫向的蝕刻量增加，不理想地導致過蝕刻，使得不可能蝕刻出確保高解析度的精細圖案。因此，難以形成精細的像素電極。 As the indium oxide layer becomes thicker, the time period required to etch the indium oxide layer in order to form a pixel electrode increases. Therefore, the amount of etching is increased not only in the longitudinal direction but also in the lateral direction, which undesirably causes over-etching, making it impossible to etch a fine pattern ensuring a high resolution. Therefore, it is difficult to form a fine pixel electrode.
帶著解決這個問題的目標，根據本發明的用於蝕刻氧化銦層的蝕刻劑組合物含有硝酸鹽化合物。 With the goal of solving this problem, the etchant composition for etching an indium oxide layer according to the present invention contains a nitrate compound.
具體而言，根據本發明的蝕刻劑組合物可以展現蝕刻較厚的氧化銦層的能力，由此降低所述氧化銦層的側蝕程度，從而防止過蝕刻，並使得有可能蝕刻精細圖案，從而實現具有高解析度的液晶顯示器。 Specifically, the etchant composition according to the present invention can exhibit the ability to etch a thicker indium oxide layer, thereby reducing the degree of side etching of the indium oxide layer, thereby preventing over-etching, and making it possible to etch fine patterns, Thus, a liquid crystal display with high resolution is realized.
此外，因為所述蝕刻劑組合物中包括所述硝酸鹽化合物，在蝕刻氧化銦層時可以最小化對下部金屬層的損害。 In addition, because the nitrate compound is included in the etchant composition, damage to the lower metal layer can be minimized when the indium oxide layer is etched.
利用根據本發明的蝕刻劑組合物蝕刻的氧化銦層具有500至1500Å的厚度，並優選900至1500Å。 The indium oxide layer etched with the etchant composition according to the present invention has a thickness of 500 to 1500 Å, and preferably 900 to 1500 Å.
此外，所述氧化銦層包括選自由氧化銦錫(ITO)層，氧化銦鋅(IZO)層，氧化銦錫鋅(ITZO)層，和氧化銦鎵鋅(IGZO)層所組成的組中的至少一種。 In addition, the indium oxide layer includes a member selected from the group consisting of an indium tin oxide (ITO) layer, an indium zinc oxide (IZO) layer, an indium tin zinc oxide (ITZO) layer, and an indium gallium zinc oxide (IGZO) layer. At least one.
所述氧化銦層之下的下層種類沒有特別的限制，但是可以包括單層，包括鉬基金屬層或鋁基金屬層，或者包括所述單層的多層。 The type of the lower layer under the indium oxide layer is not particularly limited, but may include a single layer, including a molybdenum-based metal layer or an aluminum-based metal layer, or a plurality of layers including the single layer.
下面是對根據本發明的蝕刻劑組合物的各個組分的說明。 The following is a description of each component of the etchant composition according to the present invention.
在根據本發明的蝕刻劑組合物中，硝酸(HNO3)或亞硝酸(HNO2)通過氧化和置換反應用作氧化銦層的主要蝕刻劑。 In the etchant composition according to the present invention, nitric acid (HNO 3 ) or nitrous acid (HNO 2 ) is used as a main etchant for an indium oxide layer through oxidation and displacement reactions.
基於所述蝕刻劑組合物總重量，硝酸或亞硝酸的用量是5至12wt%，並優選7至10wt%。 Based on the total weight of the etchant composition, the amount of nitric acid or nitrous acid is 5 to 12% by weight, and preferably 7 to 10% by weight.
如果硝酸或亞硝酸的量小於5wt%，則不能有效蝕刻氧化銦層，不理想地增加了蝕刻時間並產生殘渣和蝕刻缺陷。另一方面，如果硝酸或亞硝酸的量超過12wt%，則由於氮量增加導致產生較大量的廢液，不理想地增加了廢液處置成本和環境污染處理成本。 If the amount of nitric acid or nitrous acid is less than 5 wt%, the indium oxide layer cannot be effectively etched, which undesirably increases the etching time and generates residues and etching defects. On the other hand, if the amount of nitric acid or nitrous acid exceeds 12% by weight, a large amount of waste liquid is generated due to an increase in the amount of nitrogen, which undesirably increases the waste liquid disposal cost and the environmental pollution treatment cost.
在根據本發明的蝕刻劑組合物中，所述氯化合物通過取代起到所述氧化銦層的輔助蝕刻劑的作用。在蝕刻氧化銦層時，產生大量的蝕刻殘渣，所述氯化合物負責抑制殘渣的產生。 In the etchant composition according to the present invention, the chlorine compound functions as an auxiliary etchant for the indium oxide layer by substitution. When etching the indium oxide layer, a large amount of etching residue is generated, and the chlorine compound is responsible for suppressing the generation of the residue.
所述氯化合物包括選自由鹽酸、氯化鈉、氯化鉀和氯化銨所組成的組中的至少一種。 The chlorine compound includes at least one selected from the group consisting of hydrochloric acid, sodium chloride, potassium chloride, and ammonium chloride.
基於所述蝕刻劑組合物的總重量，所述氯化合物的用量是0.01至5wt%，並優選1至3wt%。 The amount of the chlorine compound used is 0.01 to 5 wt%, and preferably 1 to 3 wt%, based on the total weight of the etchant composition.
如果所述氯化合物的量小於0.01wt%，不能有效蝕刻氧化銦層，不理想地增加了蝕刻時間並產生殘渣和蝕刻缺陷。另一方面，如果所述氯化合物的量超過5wt%，則蝕刻速率過度增加，從而引起過蝕刻，由此不能充分形成驅動像素電極必要的面積。 If the amount of the chlorine compound is less than 0.01 wt%, the indium oxide layer cannot be effectively etched, and the etching time is undesirably increased and residues and etching defects are generated. On the other hand, if the amount of the chlorine compound exceeds 5 wt%, the etching rate is excessively increased to cause over-etching, and thus an area necessary for driving the pixel electrode cannot be sufficiently formed.
在根據本發明的蝕刻劑組合物中，所述硝酸鹽化合物發揮了防止在所述氧化銦層之下的下部金屬層中接觸孔的周圍部分暴露於所述蝕刻劑組合物而產生的腐蝕的作用。 In the etchant composition according to the present invention, the nitrate compound functions to prevent corrosion caused by the surrounding portion of the contact hole in the lower metal layer below the indium oxide layer from being exposed to the etchant composition. effect.
此外，當蝕刻具有500至1500Å、並優選900至1500Å厚度的氧化銦層時，所述硝酸鹽化合物還起到防止所述氧化銦層回應於蝕刻時間增加的過度側蝕的作用。 In addition, when an indium oxide layer having a thickness of 500 to 1500 Å, and preferably 900 to 1500 Å is etched, the nitrate compound also functions to prevent excessive side etching of the indium oxide layer in response to an increase in etching time.
所述硝酸鹽化合物包括選自由硝酸鈉、硝酸銨和硝酸鉀所組成的組中的至少一種。 The nitrate compound includes at least one selected from the group consisting of sodium nitrate, ammonium nitrate, and potassium nitrate.
基於所述蝕刻劑組合物的總重量，所述硝酸鹽化合物的用量是0.01至3wt%，並優選1至2.5wt%。 The amount of the nitrate compound is 0.01 to 3 wt%, and preferably 1 to 2.5 wt% based on the total weight of the etchant composition.
如果所述硝酸鹽化合物的量小於0.01wt%，不能充分防止腐蝕，不理想地引起下部金屬層的損害並增加氧化銦層的側蝕，從而使得難以形成精細圖案的氧化銦層。另一方面，如果所述硝酸鹽化合物的量超過3wt%，它可以 起到防止腐蝕的作用，但是可以降低氧化銦層的蝕刻速率並可由此產生殘渣。 If the amount of the nitrate compound is less than 0.01 wt%, it cannot sufficiently prevent corrosion, undesirably cause damage to the lower metal layer, and increase side etching of the indium oxide layer, thereby making it difficult to form a fine patterned indium oxide layer. On the other hand, if the amount of the nitrate compound exceeds 3 wt%, it can It plays a role in preventing corrosion, but it can reduce the etching rate of the indium oxide layer and cause residues.
在本發明的蝕刻劑組合物中，使用的水量要使得所述蝕刻劑組合物的總重量是100wt%。所述水沒有特別的限制，但是優選包括去離子水。特別有用的是電阻率為18MΩ．cm或更高的去離子水，電阻率表明從所述水除去離子的程度。 In the etchant composition of the present invention, the amount of water used is such that the total weight of the etchant composition is 100% by weight. The water is not particularly limited, but preferably includes deionized water. Particularly useful is the resistivity of 18MΩ. cm or higher in deionized water, the resistivity indicates how much ions are removed from the water.
根據本發明的蝕刻劑組合物還可以包括選自由掩蔽劑和抗腐蝕劑所組成的組中的至少一種。所述添加劑不限於此，並且為了更有效地展現本發明的效應，可以選擇性添加本領域已知的各種添加劑。 The etchant composition according to the present invention may further include at least one selected from the group consisting of a masking agent and an anticorrosive. The additives are not limited thereto, and in order to more effectively exhibit the effects of the present invention, various additives known in the art may be selectively added.
根據本發明的蝕刻劑組合物的組分可以利用通常已知的方法製備，並且可以具有適合於半導體加工的純度。 The components of the etchant composition according to the present invention may be prepared by a generally known method, and may have a purity suitable for semiconductor processing.
另外，本發明提出了蝕刻氧化銦層的方法，所述方法包括：(1)在基板上形成氧化銦層，(2)在所述氧化銦層上選擇性留下光敏材料，和(3)利用本發明的蝕刻劑組合物蝕刻所述氧化銦層。 In addition, the present invention provides a method for etching an indium oxide layer, the method including: (1) forming an indium oxide layer on a substrate, (2) selectively leaving a photosensitive material on the indium oxide layer, and (3) The indium oxide layer is etched using the etchant composition of the present invention.
在根據本發明的蝕刻方法中，所述光敏材料優選是通常的光刻膠材料，並且可以通過通常的曝光和顯影而選擇性留下。 In the etching method according to the present invention, the photosensitive material is preferably a general photoresist material, and can be selectively left by ordinary exposure and development.
所述氧化銦層以具有500至1500Å、並優選900至1500Å厚度的單層的形式提供。 The indium oxide layer is provided in the form of a single layer having a thickness of 500 to 1500Å, and preferably 900 to 1500Å.
所述氧化銦層包括選自由氧化銦錫(ITO)層， 氧化銦鋅(IZO)層，氧化銦錫鋅(ITZO)層，和氧化銦鎵鋅(IGZO)層所組成的組中的至少一種。 The indium oxide layer includes a layer selected from an indium tin oxide (ITO) layer, At least one of the group consisting of an indium zinc oxide (IZO) layer, an indium tin zinc oxide (ITZO) layer, and an indium gallium zinc oxide (IGZO) layer.
另外，本發明提出了製造液晶顯示器的陣列基板的方法，所述方法包括：(1)在基板上形成閘極線，(2)在包括所述閘極線的基板上形成閘極絕緣層，(3)在所述閘極絕緣層上形成氧化物半導體層，(4)在所述氧化物半導體層上形成源極電極和汲極電極，和(5)形成與所述汲極電極連接的像素電極，其中(5)包括形成氧化銦層和利用蝕刻劑組合物蝕刻所述氧化銦層，從而形成所述像素電極，並且所述蝕刻劑組合物是上文描述的蝕刻劑組合物。 In addition, the present invention proposes a method of manufacturing an array substrate for a liquid crystal display, the method comprising: (1) forming a gate line on a substrate, (2) forming a gate insulating layer on a substrate including the gate line, (3) forming an oxide semiconductor layer on the gate insulating layer, (4) forming a source electrode and a drain electrode on the oxide semiconductor layer, and (5) forming a source electrode connected to the drain electrode A pixel electrode, wherein (5) includes forming an indium oxide layer and etching the indium oxide layer with an etchant composition to form the pixel electrode, and the etchant composition is the etchant composition described above.
所述氧化銦層以具有500至1500Å、並優選900至1500Å厚度的單層的形式提供。 The indium oxide layer is provided in the form of a single layer having a thickness of 500 to 1500Å, and preferably 900 to 1500Å.
所述氧化銦層包括選自由氧化銦錫(ITO)層，氧化銦鋅(IZO)層，氧化銦錫鋅(ITZO)層，和氧化銦鎵鋅(IGZO)層所組成的組中的至少一種。 The indium oxide layer includes at least one selected from the group consisting of an indium tin oxide (ITO) layer, an indium zinc oxide (IZO) layer, an indium tin zinc oxide (ITZO) layer, and an indium gallium zinc oxide (IGZO) layer. .
在上述方法的(5)中，所述像素電極可以通過利用本發明的蝕刻劑組合物蝕刻所述氧化銦層形成。 In the above method (5), the pixel electrode may be formed by etching the indium oxide layer using the etchant composition of the present invention.
更具體地說，利用根據本發明的蝕刻劑組合物，可以以精細圖案而且沒有過度側蝕的形式蝕刻所述具有500至1500Å並優選900至1500Å厚度的氧化銦層，所述氧化銦層用於實現具有快速回應速度和高解析度的液晶顯示器，由此形成達到高解析度的像素電極。 More specifically, with the etchant composition according to the present invention, the indium oxide layer having a thickness of 500 to 1500Å and preferably 900 to 1500Å can be etched in a fine pattern without excessive side etching, and the indium oxide layer is used for In order to realize a liquid crystal display with fast response speed and high resolution, a pixel electrode with high resolution is formed.
當利用本發明的蝕刻劑組合物蝕刻氧化銦層時，可以防止對所述氧化銦層之下的下部金屬層的損害， 從而在不損害下部金屬層下形成像素電極。 When the indium oxide layer is etched by using the etchant composition of the present invention, damage to the lower metal layer under the indium oxide layer can be prevented, Thus, a pixel electrode is formed without damaging the lower metal layer.
液晶顯示裝置的陣列基板可以是薄膜電晶體(TFT)陣列基板。 The array substrate of the liquid crystal display device may be a thin film transistor (TFT) array substrate.
另外，本發明提出了通過上述方法製造的液晶顯示器的陣列基板。 In addition, the present invention proposes an array substrate for a liquid crystal display manufactured by the above method.
所述陣列基板包括通過利用根據本發明的蝕刻劑組合物蝕刻而形成的像素電極。 The array substrate includes a pixel electrode formed by etching with the etchant composition according to the present invention.
此外，除了本發明的陣列基板之外，本發明還可以提供利用上述蝕刻劑組合物製造的有機發光二極體(OLED)、觸控式螢幕(TS)或其他電子器件。 In addition, in addition to the array substrate of the present invention, the present invention can also provide an organic light emitting diode (OLED), a touch screen (TS), or other electronic devices manufactured by using the above-mentioned etchant composition.
因此，僅提出以下實施例進行說明但是不應被解釋為限制本發明，並且可以由本領域技術人員在本發明的範圍內適當修改或改變。 Therefore, only the following examples are presented for illustration but should not be construed as limiting the present invention, and may be appropriately modified or changed by those skilled in the art within the scope of the present invention.
<用於蝕刻氧化銦層的蝕刻劑組合物的製備> <Preparation of an etchant composition for etching an indium oxide layer>
實施例1至4和比較例1至7 Examples 1 to 4 and Comparative Examples 1 to 7
利用下面表1中示出的量的組分製備實施例1至4和比較例1至7的蝕刻劑組合物，並且使用的水量使得所述蝕刻劑組合物的總重量是100wt%。 The etchant compositions of Examples 1 to 4 and Comparative Examples 1 to 7 were prepared using the components in the amounts shown in Table 1 below, and the amount of water used was such that the total weight of the etchant composition was 100% by weight.
試驗例1：用於蝕刻氧化銦層的蝕刻劑組合物的性質評價Test Example 1: Property evaluation of an etchant composition for etching an indium oxide layer
在玻璃基板(100mm x 100mm)上，沉積鋁/鉬層以形成源/汲極，然後在所述鋁/鉬層上形成矽並在其中形成孔，由此暴露鋁/鉬，其是所述源/汲極的金屬層。之後，將ITO層沉積到厚度1300Å，然後進行光刻，從而形成在所述基板上具有預定圖案的光刻膠，隨後利用實施例1至4和比較例1至7的各蝕刻劑組合物蝕刻所述ITO層。 On a glass substrate (100mm x 100mm), an aluminum / molybdenum layer is deposited to form a source / drain, and then silicon is formed on the aluminum / molybdenum layer and a hole is formed therein, thereby exposing aluminum / molybdenum, which is the Source / drain metal layer. After that, an ITO layer was deposited to a thickness of 1300 Å, and then subjected to photolithography to form a photoresist having a predetermined pattern on the substrate, followed by etching with each of the etchant compositions of Examples 1 to 4 and Comparative Examples 1 to 7 ITO layer.
在蝕刻過程中，使用噴霧蝕刻機(ETCHER (TFT)，SEMES製造)，並且所述蝕刻劑組合物的溫度設置到約40℃。此外，取決於其他加工條件和其他因素，適當的溫度根據需要而變。蝕刻時間取決於蝕刻溫度而變，但是在LCD蝕刻過程中設置在約50至120秒的範圍內。 During the etching process, a spray etcher (ETCHER (TFT), manufactured by SEMES), and the temperature of the etchant composition is set to about 40 ° C. In addition, depending on other processing conditions and other factors, the appropriate temperature varies as needed. The etching time varies depending on the etching temperature, but is set in a range of about 50 to 120 seconds during LCD etching.
利用SEM(S-4700，HITACHI製造)觀察蝕刻過程中蝕刻的ITO層的橫截面輪廓，並觀察側蝕、殘渣產生和對下部金屬(Al/Mo)的侵蝕，基於以下評價標準進行評價。結果顯示在下面表2中。 The cross-sectional profile of the ITO layer etched during the etching process was observed with an SEM (S-4700, manufactured by Hitachi), and side etching, residue generation, and erosion of the lower metal (Al / Mo) were observed, and evaluation was performed based on the following evaluation criteria. The results are shown in Table 2 below.
<側蝕距離> <Side Etching Distance>
◎：小於0.2μm(優秀) ◎: less than 0.2 μm (excellent)
○：0.2至小於0.5μm(良好) ○: 0.2 to less than 0.5 μm (good)
X：0.5μm或更高或者未蝕刻(差) X: 0.5 μm or more or not etched (poor)
<殘渣產生> <Residue generation>
○：沒有殘渣(圖2) ○: No residue (Figure 2)
X：產生殘渣(圖3) X: Residue is generated (Figure 3)
<對下層的侵蝕(Al/Mo)> <Erosion to the lower layer (Al / Mo)>
○：無侵蝕(圖4) ○: No erosion (Figure 4)
X：侵蝕(圖5) X: erosion (Figure 5)
從表2的結果顯而易見，實施例1至4的蝕刻劑組合物，其使用基於所述蝕刻劑組合物的總重量為0.01至3wt%量的硝酸鹽化合物，觀察到側蝕小於0.2μm，既沒有發生殘渣也沒有發生對下層的侵蝕。 It is clear from the results in Table 2 that the etchant compositions of Examples 1 to 4 used a nitrate compound in an amount of 0.01 to 3 wt% based on the total weight of the etchant composition, and observed that the side etch was less than 0.2 μm, both No residues or erosion of the lower layer occurred.
然而，在不含硝酸鹽化合物的比較例1的蝕刻劑組合物中，產生過度的側蝕，並觀察到殘渣和對下層的侵蝕，並且在比較例2的蝕刻劑組合物中觀察到對下層的侵蝕。 However, in the etchant composition of Comparative Example 1 which did not contain a nitrate compound, excessive side etching was generated, and residues and erosion on the lower layer were observed, and on the lower layer was observed in the etchant composition of Comparative Example 2. Erosion.
此外，在分別包括硫酸鉀和乙酸銨代替所述硝酸鹽化合物的比較例3和4的蝕刻劑組合物中，沒有產生殘渣，但是觀察到過度的側蝕和對下層的侵蝕。 In addition, in the etchant compositions of Comparative Examples 3 and 4 including potassium sulfate and ammonium acetate, respectively, in place of the nitrate compound, no residue was generated, but excessive side etching and erosion to the lower layer were observed.
在使用硝酸的量基於蝕刻劑組合物的總重量超過12wt%的比較例5的蝕刻劑組合物中和在使用氯化合物的量超過5wt%的比較例6的蝕刻劑組合物中，既沒有觀察到殘渣也沒有對下層的侵蝕，但是產生過度的側蝕。 In the etchant composition of Comparative Example 5 in which the amount of nitric acid was more than 12 wt% based on the total weight of the etchant composition, and in the etchant composition of Comparative Example 6 in which the amount of chlorine compound was used was more than 5 wt%, neither was observed There is no erosion of the lower layer to the residue, but excessive side erosion occurs.
此外，在使用硝酸鹽化合物的量基於所述蝕刻劑 組合物的總重量超過3wt%的比較例7的蝕刻劑組合物中，限制了側蝕並且不侵蝕下層，但是產生殘渣。 In addition, the amount of nitrate compound used is based on the etchant In the etchant composition of Comparative Example 7 in which the total weight of the composition exceeded 3% by weight, side etching was restricted and the lower layer was not eroded, but residue was generated.
因此，包括基於蝕刻劑組合物的總重量為0.01至3wt%量的硝酸鹽化合物的根據本發明的蝕刻劑組合物，具有蝕刻厚氧化銦層的高能力，並且能夠蝕刻所述氧化銦層而不損害佈置在所述氧化銦層之下的下層。 Therefore, the etchant composition according to the present invention including a nitrate compound in an amount of 0.01 to 3 wt% based on the total weight of the etchant composition has a high ability to etch a thick indium oxide layer and is capable of etching the indium oxide layer. The underlying layer disposed under the indium oxide layer is not damaged.
雖然已經出於說明性的目的公開了本發明的優選實施方式，但本領域技術人員將領會，在不背離所附申請專利範圍中公開的本發明的範圍和精神之下，各種修改、添加和取代是可能的。 Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and changes may be made without departing from the scope and spirit of the present invention as disclosed in the scope of the attached application patent. Replacement is possible.
Claims (10)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ??10-2015-0025012 | 2015-02-23 | ||
| KR1020150025012A KR102282955B1 (en) | 2015-02-23 | 2015-02-23 | Etching solution composition for indium oxide layer and manufacturing method of an array substrate for Liquid crystal display using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW201634666A TW201634666A (en) | 2016-10-01 |
| TWI666302B true TWI666302B (en) | 2019-07-21 |
Family
ID=56744398
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW105102697A TWI666302B (en) | 2015-02-23 | 2016-01-28 | Etchant composition for indium oxide layer, method of etching, an array substrate for liquid crystal display and manufacturing method thereof using the same |
Country Status (3)
| Country | Link |
|---|---|
| KR (1) | KR102282955B1 (en) |
| CN (2) | CN105907396A (en) |
| TW (1) | TWI666302B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113026019B (en) * | 2017-05-22 | 2024-01-26 | 东友精细化工有限公司 | Silver thin film etching liquid composition, etching method and metal pattern forming method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103911156A (en) * | 2012-12-28 | 2014-07-09 | 东友精细化工有限公司 | Etchant composition for metallic oxide layer |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB499627A (en) * | 1937-04-08 | 1939-01-26 | Aluminium Walzwerke Singen | Improvements in and relating to methods of making electrodes for electrolytic condensers |
| JPH02111886A (en) * | 1988-10-18 | 1990-04-24 | Sumitomo Special Metals Co Ltd | Etching solution for partially al clad sheet for lead frame |
| JP2002184748A (en) * | 2000-12-12 | 2002-06-28 | Matsushita Electric Ind Co Ltd | Etching liquid and etching method using it |
| KR20070053957A (en) * | 2005-11-22 | 2007-05-28 | 주식회사 동진쎄미켐 | Etching composition for ito |
| KR101294968B1 (en) * | 2006-11-20 | 2013-08-09 | 동우 화인켐 주식회사 | Etching solution composition and method of etching using the etching solution composition |
| KR20090082772A (en) * | 2008-01-28 | 2009-07-31 | 주식회사 동진쎄미켐 | Etchant composition for indium tin oxide layer and etching method using the same |
| KR101507159B1 (en) * | 2008-09-02 | 2015-03-31 | 동우 화인켐 주식회사 | Manufacturing method of array substrate for liquid crystal display |
| JP5767796B2 (en) * | 2010-09-28 | 2015-08-19 | 林純薬工業株式会社 | Etching solution composition and etching method |
| KR101774484B1 (en) | 2011-02-15 | 2017-09-05 | 삼성디스플레이 주식회사 | Non-halogenated etchant for etching an indium oxide layer and method of manufacturing a display substrate using the non-halogenated etchant |
| KR20130084717A (en) * | 2012-01-18 | 2013-07-26 | 솔브레인 주식회사 | Etchant composition and method of manufacturing a display substrate using the etchant composition |
| CN102732252A (en) * | 2012-06-21 | 2012-10-17 | 江阴润玛电子材料股份有限公司 | Novel aqua regia system ITO (indium tin oxide) etching solution and its preparation method |
| CN102732253A (en) * | 2012-06-30 | 2012-10-17 | 江阴润玛电子材料股份有限公司 | Ferric trichloride ITO etching solution and its preparation method |
| KR101953215B1 (en) * | 2012-10-05 | 2019-03-04 | 삼성디스플레이 주식회사 | Etchant composition, metal wiring and method of manufacturing a display substrate |
| KR20140086666A (en) * | 2012-12-28 | 2014-07-08 | 동우 화인켐 주식회사 | Etchant composition for metal oxide layer |
-
2015
- 2015-02-23 KR KR1020150025012A patent/KR102282955B1/en active IP Right Grant
-
2016
- 2016-01-28 TW TW105102697A patent/TWI666302B/en active
- 2016-02-04 CN CN201610079267.3A patent/CN105907396A/en active Pending
- 2016-02-04 CN CN201910679544.8A patent/CN110484258B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103911156A (en) * | 2012-12-28 | 2014-07-09 | 东友精细化工有限公司 | Etchant composition for metallic oxide layer |
Also Published As
| Publication number | Publication date |
|---|---|
| KR102282955B1 (en) | 2021-07-28 |
| KR20160102662A (en) | 2016-08-31 |
| CN105907396A (en) | 2016-08-31 |
| CN110484258A (en) | 2019-11-22 |
| CN110484258B (en) | 2022-01-14 |
| TW201634666A (en) | 2016-10-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8052889B2 (en) | Etchant composition, and methods of patterning conductive layer and manufacturing flat panel display device using the same | |
| KR101905195B1 (en) | Etchant composition for Ag thin layer and method for fabricating metal pattern using the same | |
| TW201634754A (en) | Etchant composition for silver thin layer, method of forming metal pattern using the same and method of manufacturing an array substrate using the same | |
| KR20140063283A (en) | Etchant composition for ag thin layer and method for fabricating metal pattern using the same | |
| KR20090081938A (en) | Etchant composition for Ag thin layer and method for fabricating metal pattern using the same | |
| KR101406362B1 (en) | Etchant composition for Ag thin layer and method for fabricating metal pattern using the same | |
| TWI636157B (en) | Etching solution composition for silver layer and display substrate using the same | |
| KR20140063284A (en) | Etchant composition for ag thin layer and method for fabricating metal pattern using the same | |
| KR20080045403A (en) | Etching solution composition and method of etching using the etching solution composition | |
| KR20140082186A (en) | Etchant composition for Ag thin layer and method for fabricating metal pattern using the same | |
| TWI666302B (en) | Etchant composition for indium oxide layer, method of etching, an array substrate for liquid crystal display and manufacturing method thereof using the same | |
| KR20140091401A (en) | array substrate for liquid crystal display device and fabricating method of the same | |
| TWI673344B (en) | Etching solution composition for indium oxide layer and method for manufacturing array substrate for liquid crystal display device using the same | |
| KR20190002381A (en) | Etchant composition for Ag thin layer and method for fabricating metal pattern using the same | |
| KR101329824B1 (en) | Manufacturing method of array substrate for liquid crystal display | |
| KR101151952B1 (en) | Etching solution of Indium Oxide film and etching method thereof | |
| KR20080009865A (en) | High etch rate indium oxide etchant | |
| KR102068964B1 (en) | array substrate for liquid crystal display device and fabricating method of the same | |
| TWI665289B (en) | Etchant composition for indium oxid layer, method for manufacturing array substrate for liquid crystal display device, array substrate for liquid crystal display device and wire | |
| KR100595910B1 (en) | Etchant composition for pixel layer of FPD | |
| CN110295367B (en) | Silver film etching liquid composition, etching method using the same and metal pattern forming method | |
| KR102459686B1 (en) | Etching solution composition and preparing method of an array substrate for display using the same | |
| CN117467443A (en) | Etching liquid composition and display panel | |
| KR102303076B1 (en) | Etching solution composition for indium oxide layer and manufacturing method of an array substrate for liquid crystal display using the same | |
| CN114106835A (en) | Etching solution composition and display panel |